Production of organic sulphur compounds



Patent ed Dec. 20, 1938 I I s UNITED STATES PATENT OFFICE I PRODUCTION OF ORGANIC SULPHUR COMPOUNDS Hanna Ufer and Otto Hecht, Ludwigshaien-onthe-Rhine, Germany, assignors to I. G. Farbenindustrie Aktiengeselischaft, Frankfort-an the- Main, Germany No Drawing. Application April 11, 1936, Serial No. 73,932. In Germany April 17, 1935 13 Claims. (01. 260-513) The present invention relates to organic sulpractice but the invention is not restricted to phur compounds and to a process of producing the these examples. The parts are by weight. same.

We. have found that vinyl sulphides or vinyl Example 1 5 sulphoxides of the general formulae Parts Of v ny Da -110 34 s p cxi e and 20 6 R(S CH CH2) parts of a from 38 to 40 per cent solutionoi sodium bisulphite are heated for about four hours and R(SO.CH=CH:), in which R is'an aliphatic, at about 100 C. under reflux while stirring conisocyclic or heterocyclic radicle and a: is a whole tinuously or periodically. The sulphoxide, origi- 10 number, can be reacted with watersol'uble bisulnally floating on the aqueous layer, gradually 10 phites of light metals, such as sodium, potassium, passes into solution. After coo1ing, the crystal calcium and magnesium. The bisulphite adds pulp formed is separated from the mother liquor on to the vinyl sulphide or vinyl sulphoxide group and washed with ether to remove unchanged with the formation of sulphonic acid salts. In initial material. i

16' order to render the reaction complete and to ob- The reaction product is obta'myd inthe form tain goodyields, the reaction components must of colorless crystals which dissolve readily in be heated for a sufiiciently long period or at a water and may be recrystallized from alcohol. suiilciently high temperature. Heating at from The corresponding addition products may be about 70 to 130 for several hours is usually sufllobtained in a. similar manner from other isocyclic 20 .cient. or heterocyclic vinyl sulphoxides. 30 V For the reaction it is possible to employ vinyl Emmple z sulphides and vinyl sulphoxides of the formulae R(s.cH=cH- d R(SO CH='CH3) i which R 100 parts of octodecyl vinyl sulphoxide and 250 1 an alkyl r alkenyl gmup, as 'for example parts of an about 40 per cent solution of sodium '25 ethyl, propyl, butyl, hexyl, dodecyl, octodecyl or blsulphite are heated for about four hours at octodecenyl group, the radicle of an isocyclic about undel h sulphoxide compound, as for example a phenyl, naphthyl, passes into solution rather rapidly. After coolbenzyl, phenyl-ethyl, cyclohexyl or tetrahydrothe resulting c ystal p p is p a d rom naphthyl residue, or the radicle of a heterocyclic the mother liquor and t d with e er for the compound, a for example of idi i li removal 01 small amounts of unchanged initial 80 benzothiazole or benzimidazole. The said vinyl a a The resulting d n pr duct may sulphides or vinyl sulphoxides may also contain be further rifi by crystallization from alcoth S CH=CI-Ig rs0 c1-1=c groups t hol. It forms colorless crystals, comparatively more times, and may then react 9, corresponding readily soluble in warm water, and has a StlOtlg number of times. They may also contain other u s f i p w r for a pl f r ar mat hy- 35 atoms or atomic groups, as for example halogen drocarbcnsatoms or hydroxyl, alkyl, alkoxy,'hydroxyalky1, If otheraliphaticvinyl sulphoxides, as for ex- .nitro, amino, sulph-hydryl, carboxylic or sulamp y d y 0r octcdecenyl v nyl sulphonic id phoxides, be employed instead of octodecyl vinyl 40- The reaction is preferably carried out in the D d flolflespcnding addition compounds 40 presence of solvents or diluents, such as water or are obtained in a similar manner.

aqueous alcoh01s,it desired under pressure. When employing potassium or calcium bisul- The compounds obtained may be employed'for phite instead of sodium bisulphite the potassium example for the manufacture of dyestufis or, when or calcium salts of the said sulphide or sulphoxide employing suitable initial materials, as dyestuffs ethane sulphonic acids are ohtained- 45 themselves, and also as assistants. in the textile Example 3 and related industries. t

By further oxidation, the sulphides or sulphox- 100 Parts octodecyl V yl sulp (having a .ides containing sulphonic acid groups thus obmelting point of from 33 to 34 C.) and 240 partstained may be converted into the corresponding 01 an about 42 per cent solution of sodium bisul- 50 sulphones, or the sulphoxides may be converted by Dhi are heated r ht h urs at about 100 C. means of reducing agents into the corresponding under reflux While Stirring- After l n he sulphides. resulting crystal pulp is filtered off by suction The following examples will further illustrate and washed with ether for the removal of un- 86 how the said invention may be carried out ,in changed initial material. The product treated with ether may be recrystallized from alcohol for the purpose of further purification. The new compound is difllcultly soluble in cold water.

25 parts of vinyl para-tolyl sulphide (boiling point from 91" to 93 C. at from 9 to 10 millimetres (mercury gauge)) and 105 parts of an about 40 per cent solution of sodium bisulphite are heated for ten hours at about 100 C. under reflux while stirring continuously. I

The solid product deposited after cooling is filtered of! by suction and washed with acetone to remove unchanged initial material. The product thus obtained is soluble in water and decomposes when heated above 165 C. and thereby becomes brown.

- The yield may be increased by heating the components at a higher temperature while employing increased pressure.

Example 5 A mixture of 40 parts of 1,12-octodecane divinyl disulphoxide of about 90 per cent strength (obtained from ricinoleic acid by way of the inter- 150 parts of a saturated aqueous solution of sodium bisulphite are added to 54 parts of dodecyl vinyl sulphoxide and the mixture is heated for seven and a half hours at about 95 C. To the reaction mixture there are added 36,4 parts of sodium bicarbonate and a little water. By extracting the dried crude product with boiling al-, cohol, white crystals are obtained which decompose at from 205 to 210 C. without melting. They are readily soluble in water and possess a high foaming power and soap-like character.

Example 7 137 parts of a 34.5 per cent aqueous suspension of a mixture ofvinyl sulphoxides of high molecular weight, obtained from the mixture of sperm oil fatty acids by way of the intermediate stages of the corresponding alcohols, mercaptans and vinyl sulphides, are heated for seven hours with 109 parts of a 42 per cent sodium bisulphite solution at from about 80 to 95 C. under reflux cooling. The aqueous solution obtained having an acid reaction is adjustedto a pH-value of 7.4 by the addition of 20 parts of sodium bicarbonate. The reaction product obtained possesses a soap-like character.-

What we claim is:

1. The process of producing organic sulphur compounds which comprises reacting sulphur com- T-pounds otherwise stable under the reaction conditions obtaining and having the general formula R(YCH=CH2) in which R. is a member selected from the group consisting of radicles of aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbons and their haiogen-, hydroxyl, alkoxy. hydroxy alkyl, nitro, amino. sulphhydryl, carboxylic and sulphonic acid substitution products, a: is a whole number up to 2 and Y stands for a member selected from the group consisting of S and S0 with bisulphites of metals selected from the group consisting of sodium, potassium and calcium.

2. The process of producing organic sulphur compounds which comprises reacting sulphur compounds otherwise stable under the reaction conditions obtaining and having the general formula in which R. is a member selected from the group consisting of radicles of aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbons and their halogen-, hydroxyl, alkoxy, hydroxyalkyl, nitro, amino, sulphhydryl, carboxylic and sulphonic acid substitution products, a: is a whole number up, to 2 and Y stands for a'member selected from the group consisting of S and SO with bisulphites of light metals selected from the group consisting of sodium, potassium and calcium in the presence of inert diluents.

3. The process of producing organic sulphur compounds which comprises reacting sulphur compounds otherwise stable under the reaction conditions obtaining and having the general formula in which R is a member selected from the group consisting of radicles of aliphatic, cycloallphatic,

aliphatic-aromatic and aromatic hydrocarbons and their halogen-, hydroxyl, :alkoxy hydroxyalkyl, nitro, amino, sulphhydryl, carboxylic and sulphonic acid substitution products, a: is a whole number upto 2 and Y stands for a member selected from the group consisting of S and SO with bisulphites of light metals selected from the class consisting of sodium, potassium and calcium in the presence or water.

4. The process of producing organic sulphur compounds which comprises heating sulphur compounds otherwise stable under the reaction conditions obtaining and having the general formula in which R is a member selected from the group consisting of radicles of aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbons and their halogen-, hydroxyl, alkoxy, hydroxyalkyl, 'nitro, amino, sulphhydryl, carboxylic and sulphonic acid substitution products, a: is a whole number up to 2 and Y stands for a member selected from the group consisting of S and S0 with bisulphites of light metals selected from the class consisting of sodium, potassium and calcium at from 70 to C.

5. The process of producing organic sulphur compounds which comprises reacting a vinyl sulphoxide of the general formula R(SO.CH=CH2)'2 in which R. is an aliphatic radicle containing at least 6 carbon atoms and a: is a whole number up to 2 with bisulphites of light metals selected from the class consisting of sodium, potassium and calcium.

6. The process of producing organic sulphur compounds which comprises reacting dodecyl vinyl sulphoxlde with sodium bisulphite.

7. The process of producing organic sulphur compounds which comprises reacting octodecyl vinyl s ulphoxide with sodium bisulphite.

8. The process of producing organic sulphur compounds which comprises reacting octodecenyl vinyl sulphoxide with sodium bisulphite.

9. Stable sulphoxide-ethyl-sulphonic acid salts having the general formula in which R is a member selected from the group consisting of radicles of aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbons and their halogen-, hydroxyl, alkoxy, hydroxyalkyl, nitro, amino, sulphhydryl, carboxylic and sulphonic acid substitution products, He is a metal selected from the group of sodium, potassium and calcium and z is a whol number up to 2. a

3 1o. Bulphoxide-cthyl-sulphonic acid salts having the general formula madam-caisson),

in which R is'an aliphatic radicle containing at least 6 carbon atoms. Me is a metal selected from the group consisting of sodium, potassium and calcium and a: is a whole number up to 2.

l1. Dodecyl sulphoxide ethyl sulphonic acid sodium salt.

12. Octodecyl-sulphoxide-ethyl-sulphonic sodium salt.

13. Octodecenyl -su1phorxide ethyl sulphonic acid sodium 'salt.

HANNS UFlilR. Q'ITO HECH'I.

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